RU2666537C2 - Aqueous dispersion of copolymer - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present invention relates to an aqueous dispersion for the preparation of coating materials, to a water-borne base coat suitable for coating automotive bodies and/or parts for mounting on automotive bodies, method for producing a multilayer color and/or for a color system effect, and method for preparing an aqueous dispersion. Said aqueous dispersion comprises at least one copolymer obtained by polymerizing olefinically unsaturated monomers in the presence of an aqueous dispersion of polyurethane using a water soluble initiator. Olefinically unsaturated monomers are dosed so that their concentration in the reaction solution does not exceed 6.0 wt% during the entire reaction time, based on the total amount of olefinically unsaturated monomers. Mixture of olefinically unsaturated monomers includes at least one polyolefinically unsaturated monomer.

EFFECT: coatings produced using these dispersions have a high limit for the occurrence of pinholes and, consequently, the smallest number of surface defects, as well as improved adhesion in the case of multi-layer finishing.

17 cl, 4 dwg, 6 tbl, 6 ex

Description

The present invention relates to aqueous dispersions of copolymers, and to their preparation and use, especially in the field of auto-mechanical finishing.

The prior art discloses copolymers having a core / shell structure.

Document EP 1218434 B1 discloses a grafted copolymer based on polyurethane and their use for the production of coating materials, adhesives and sealing compounds.

Documents EP 1185568 B1 and EP 1173491 B1 describe copolymers having a core / shell structure, the outer part of which is completely crosslinked, where the core consists of polyacrylate and the shell may consist of polyurethane.

EP 1 330 480 B1 describes copolymers where the core consists of sulfide-containing polyurethanes and a polyacrylate shell.

The copolymers known from the prior art are in the form of aqueous dispersions and can be used to produce aqueous coating materials, especially for waterborne basecoats.

These waterborne basecoats can be applied in the so-called basecoat / self-healing coating method, the wet coating method without pre-drying, for color coating and / or coating for the effect of a multi-layer paint system.

Known methods need improvement, especially regarding the appearance of tiny holes visible as very small holes in a self-healing coating and coating base. The ability to conceal small marks and adhesion in the case of a multilayer finish is not appropriate in the case of coatings known from the prior art.

The objective which underlies the present invention, therefore, is to provide an aqueous dispersion of a copolymer of the type described above, which can be applied to a binder layer of a color and / or the effect of a multilayer ink system, improved compared with the prior art.

More specifically, this layer should have only very few tiny holes, if any, and / or a higher limit for the occurrence of pinholes. The pinhole puncture limit refers to the thickness of the dry basecoat, above which tiny holes appear. At the same time, the ability to hide small marks and adhesion in the case of multilayer finishing, for example, in the form of repeated final finishing, should be improved.

It was found that, unexpectedly, the complex task underlying this invention was achieved by providing

an aqueous dispersion comprising at least one copolymer, a copolymer, which is obtained in the following way

(I) initially loaded with an aqueous dispersion of at least one polyurethane, and then

(II) polymerizing a mixture of olefinically unsaturated monomers in the presence of polyurethane from (I),

Where

(a) a water soluble initiator is used,

(b) the metered addition of olefinically unsaturated monomers is carried out in such a way that a concentration of 6.0 wt. %, in terms of the total number of olefinically unsaturated monomers in the reaction solution is not exceeded during the entire duration of the reaction, and

(c) the mixture of olefinically unsaturated monomers comprises at least one polyolefinically unsaturated monomer.

The invention also relates to a method for producing invented dispersions, to the use of these aqueous dispersions in coating materials, especially base coatings, to waterborne materials, base coatings including the aforementioned dispersions, and to a method for producing multilayer paint systems.

Tiny holes are very small holes in the self-healing coating and coating base that are visible in the finished coating. They are one of the most common surface defects when applying aerosol paints. Defects called tiny openings in the description and available examples that follow are characterized by funnel-shaped openings that extend into cylindrical tubes in order of bubble print size, which have an average opening diameter of the funnel of approximately 300-700 μm and an average diameter of the tube of approximately 15-60 μm, and and pass through a self-healing coating and a base coating until reaching a lower coating. They may be the result of escaping gases such as trapped air or evaporating liquids.

The term "(meth) acrylate" should refer hereinafter to both acrylate and methacrylate.

A copolymer in the context of the present invention relates to polymer particles formed from different polymers. It explicitly includes both polymers bonded covalently to each other and those in which different polymers are bonded to each other by adhesion. Combinations of the two types of bindings are also covered by this definition.

The invented dispersions and the method for producing these dispersions are characterized by the stages of their preparation.

In a first production step, an aqueous dispersion of a polyurethane resin is initially charged.

Suitable saturated or unsaturated polyurethane resins are described, for example, in

- German patent application DE 19948004 A1, page 4 line 19 - page 11 line 29 (polyurethane prepolymer B1)

- European patent application EP 0228003 A1, page 3 line 24 - page 5 line 40,

- European patent application EP 0634431 A1, page 3 line 38 - page 8 line 9, or

- international patent application WO 92/15405, page 2 line 35 - page 10 line 32.

To obtain a polyurethane resin, preference is given to the use of aliphatic, cycloaliphatic, aliphatic-cycloaliphatic, aromatic, aliphatic-aromatic and / or cycloaliphatic-aromatic polyisocyanates known to those skilled in the art. Particular preference is given to aliphatic and aliphatic-cycloaliphatic polyurethane resins.

The alcohol components used to make the polyurethane resins are preferably saturated and unsaturated polyols known to those skilled in the art, and optionally, in small amounts, also monoalcohols. Especially diols and, optionally, in small quantities, triols are used for the emergence of industries. Examples of suitable polyols are saturated or olefinically unsaturated polyester polyols and / or polyester polyols. The polyols used are especially polyester polyols, especially those which have an average molecular weight of 400 to 5000 g / mol (measured by osmometry using vapor pressure).

Preferably, the polyurethane initially loaded into the aqueous dispersion is a hydrophilically stabilized polyurethane. For hydrophilic stabilization or to increase the ability to disperse in an aqueous medium, the polyurethane resin may contain specific ionic groups and / or groups that can be converted into ionic groups (potentially ionic groups). Such polyurethane resins are referred to in the context of the present invention as ionically hydrophilically stabilized polyurethane resins. Similarly, nonionic hydrophilically modified groups may be present. Preference is nevertheless given to ionically hydrophilically stabilized polyurethanes. More specifically, modifiable groups are

- functional groups that can be converted into cations using neutralizing agents and / or quaternizing agents, and / or cationic groups (cationic modification)

or

- functional groups that can be converted into anions using neutralizing agents, and / or anionic groups (anionic modification)

or

- nonionic hydrophilic groups (nonionic modification)

or

- combinations of the above groups.

As is known to those skilled in the art, functional groups for cationic modification are, for example, primary, secondary and / or tertiary amino groups, secondary sulfide groups and / or tertiary phosphine groups, especially tertiary amino groups and secondary sulfide groups (functional groups that may be converted to cationic groups using neutralizing agents and / or quaternizing agents). Mention should additionally be made to cationic groups derived from the aforementioned functional groups using neutralizing agents and / or quaternizing agents known to those skilled in the art, such as primary, secondary, tertiary and / or quaternary ammonium groups, tertiary sulfonium groups and / or quaternary phosphonium groups, especially quaternary ammonium groups and tertiary sulfonium groups.

It is known that functional groups for anionic modification are, for example, carboxylic acid, sulfonic acid and / or phosphonic acid groups, especially carboxylic acid groups (functional groups that can be converted to anionic groups using neutralizing agents), and anionic groups, derived from the aforementioned functional groups using neutralizing agents known to those skilled in the art, such as carboxylate, sulfonate and / or phosphonate groups.

The functional groups for the nonionic hydrophilic modification are preferably poly (oxyalkylene) groups, especially poly (oxyethylene) groups.

Hydrophilic ionic modifications can be introduced into the polyurethane resin using monomers containing ionic or potentially ionic groups. Nonionic modifications are introduced as side or end groups into polyurethane molecules, for example, through the inclusion of poly (ethylene oxide) polymers. Hydrophilic modifications are introduced, for example, using compounds containing at least one isocyanate-reactive group, preferably at least one hydroxyl group. To introduce an ionic modification, monomers can be used which, like the modified groups, contain at least one hydroxyl group. For the introduction of nonionic modifications, preference is given to the use of polyethers of diols and / or alkoxy poly (oxyalkylene) alcohols known to a person skilled in the art.

Preference is given to adding at least one solvent to the initially loaded polyurethane dispersion, the solvent is miscible in any respect with water and in any respect with a mixture of olefinically unsaturated monomers. Particularly suitable solvents are N-methylpyrrolidone, N-ethylpyrrolidone and ethers alcohols, such as especially methoxypropanol.

As the next step in the preparation, the polymerization of a mixture of olefinically unsaturated monomers is carried out in the presence of polyurethane by the methods of so-called free radical emulsion polymerization in the presence of at least one polymerization initiator.

The polymerization initiator used should be a water soluble initiator. Examples of suitable initiators are potassium peroxodisulfate, sodium peroxodisulfate or ammonium peroxodisulfate, and also hydrogen peroxide, tert-butyl hydroperoxide, 2,2'-azobis (2-amidoisopropane) dihydrochloride, 2,2'-azobis (N, N'-dimethylene isobutidine) dihydrochloride or 2,2'-azobis (4-cyanopentanoic acid). The initiators are used either singly or in a mixture, for example, a mixture of hydrogen peroxide and sodium persulfate.

It is also possible to use known redox initiator systems as polymerization initiators. Such initiator redox systems contain at least one peroxide-containing compound in combination with a redox initiator, for example, reducing sulfur compounds, for example, bisulfites, sulfites, thiosulfates, dithionites or alkali metal tetrathionates and ammonium compounds, sodium hydroxymethanesulfinate dihydrate and / or thiourea. For example, it is possible to use combinations of peroxodisulfates with alkali metal or ammonium hydrosulfites, for example, ammonium peroxodisulfate and ammonium disulfite. The mass ratio of peroxide-containing compounds to redox co-initiators is preferably from 50: 1 to 0.05: 1. In combination with initiators or initiator redox systems, it is additionally possible to use transition metal catalysts, for example, iron salts, nickel salts, cobalt salts, manganese salts, copper salts, vanadium salts or chromium salts such as iron (II) sulfate , cobalt (II) chloride, nickel (II) sulfate, copper (I) chloride, manganese (II) acetate, vanadium (III) acetate, manganese (II) chloride. In terms of monomers, these transition metal salts are usually used in amounts of 0.1-1000 ppm. For example, it is possible to use combinations of hydrogen peroxide with iron (II) salts, for example, 0.5-30% hydrogen peroxide and 0.1-500 ppm. . salt of mora.

The initiators are preferably used in an amount of 0.05-20 wt. %, preferably 0.05-10 wt. %, more preferably 0.1-5 wt. %, calculated on the total weight of olefinically unsaturated monomers.

The result of using a water-soluble initiator is that olefinically unsaturated monomers, which are added to the initially loaded aqueous dispersion, can react immediately to provide oligomers. These oligomers have a lower tendency to penetrate the polyurethane particles in the initially charged dispersion than smaller monomers.

The polymerization is accordingly carried out at a temperature of 0-160 ° C, preferably 60-95 ° C.

In this context, preference is given to working with the exclusion of oxygen, preferably in a stream of nitrogen. In general, the polymerization is carried out at standard pressure, but it is also possible to use lower pressures or higher pressures, especially when polymerization temperatures above the boiling point of the monomers and / or solvents are used.

The invented polymers are obtained by free radical aqueous emulsion polymerization, and it is possible to add surfactants or protective colloids to the reaction medium. A list of suitable emulsifiers and protective colloids can be found, for example, in Houben Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], volume XIV / 1 Makromolekulare Stoffe [Macromolecular substances], Georg Thieme Verlag, Stuttgart 1961, p. 411 ff.

An important factor for obtaining the invented aqueous dispersion is the regulation of the polymerization reaction conditions of the mixture of olefinically unsaturated monomers in the presence of polyurethane. This is accomplished by the "precision metered polymerization" method.

Precisely metered polymerization in the context of the present invention is considered as one which is emulsion polymerization in which the content of residual monomers in the reaction solution is minimized throughout the reaction, indicating that the olefinically unsaturated monomers are dosed in such a way that a concentration of 6.0 wt. %, preferably 5.0 wt. %, more preferably 4.0 wt. %, in the reaction solution, in each case, in terms of the total number of olefinically unsaturated monomers, is not exceeded during the entire duration of the reaction.

The concentration of monomers in the reaction solution can be determined here by gas chromatography.

The concentration of monomers in the reaction solution, also referred to herein as free monomers, can be controlled in various ways.

One means of keeping the concentration of free monomers at a low level is to select a very low dosing rate for the olefinically unsaturated monomer mixture. When the rate of dosed addition is sufficiently low, all monomers can react very quickly, as soon as they are in the reaction solution, this makes it possible to ensure that the concentration of free monomers is minimized.

As well as the dosing rate, it is important that enough free radicals are always present in the reaction solution, so that dosed monomers can each react very quickly. To this end, the reaction conditions should preferably be selected so that the initiator feed is already started before the start of the metered addition of olefinically unsaturated monomers. Preference is given to starting the metered addition at least 5 minutes earlier, more preferably at least 10 minutes earlier. Preferably, at least 10 wt. %, more preferably at least 20 wt. %, most preferably at least 30 wt. %, initiator, in each case, in terms of the total amount of initiator, is added before the start of dosed addition of olefinically unsaturated monomers.

The amount of initiator is an important factor for the sufficient presence of free radicals in the reaction solution. The amount of initiator should be chosen so that enough free radicals are available at any time, so that dosed monomers can react. If the amount of initiator increases, it is also possible that higher amounts of monomers react at the same time.

An additional factor that determines the reaction rate is the structure of the monomers.

The concentration of free monomers, in this way, can be controlled through the relationship of the amount of initiator, the rate of addition of initiator, the rate of addition of monomers, and through the choice of monomers. And slowing the dosed addition and increasing the amount of initiator, as well as the early start of the addition of initiator, serve the goal of maintaining the concentration of free monomers below the above limits.

At any point in the reaction, the concentration of free monomers can be determined by gas chromatography. Typical parameters for determination are as follows: 50 m capillary column with silicon dioxide with a phase of polyethylene glycol or 50 m capillary column with silicon dioxide with a phase of polydimethylsiloxane, carrier gas helium, injector for introducing samples with flow division 150 ° C, thermostat temperature 40-220 ° C, flame ionization detector, detector temperature 275 ° C, internal standard isobutyl acrylate.

Since any concentration of free monomers that is close to the limit for precision metered polymerization should be determined by this analysis, for example, due to the very low level of reactive olefinically unsaturated monomers, the above parameters can be used to control the reaction. In this case, for example, the dosage rate of the monomers can be reduced or the amount of initiator can be increased.

Suitable olefinically unsaturated monomers may be mono- or polyolefinically unsaturated.

Examples of suitable monoolefinically unsaturated monomers include mono-olefinically unsaturated monomers based on (meth) acrylate, vinyl monoolefinically unsaturated monomers, alpha-beta unsaturated carboxylic acids, and allyl compounds.

Monoolefinically unsaturated monomers based on (meth) acrylate can, for example, be (meth) acrylic acid and esters, nitriles, or (meth) acrylic acid amides.

Preference is given to esters of (meth) acrylic acid having an olefinic unsaturated radical R.

или

or

The radical R may be aliphatic or aromatic. The radical R is preferably aliphatic.

The radical R can be, for example, an alkyl radical, or contain heteroatoms. Examples of R radicals containing heteroatoms are ethers. The radical R is preferably an alkyl radical.

If R is an alkyl radical, it may be a linear, branched or cyclic alkyl radical. In all three cases, the alkyl radicals may be unsubstituted alkyl radicals or alkyl radicals substituted with functional groups. The alkyl radical preferably has 1-20, more preferably 1-10, carbon atoms.

Particularly particularly suitable monounsaturated esters of (meth) acrylic acid having an unsubstituted alkyl radical are methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, ethylhexyl (meth) acrylate, 3,3,5-trimethylhexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, cycloalkyl (meth) acrylates such as cyclopentyl (meth) acrylate, isobornyl (meth) acrylate and cyclohexyl (meth) acrylate, o Very particular preference is given to n- and tert-butyl (meth) acrylate and methyl methacrylate.

Suitable monounsaturated esters of (meth) acrylic acid having a substituted alkyl radical may preferably be substituted with one or more hydroxyl groups.

Particularly particularly suitable monounsaturated esters of (meth) acrylic acid having an alkyl radical substituted with one or more hydroxyl groups are 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3 -hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.

Vinyl monounsaturated monomers can be monomers having an olefinic unsaturated radical R 'on a vinyl group.

The radical R 'may be aliphatic or aromatic, preference is given to aromatic radicals.

The radical R ′ may be a hydrocarbyl radical or contain heteroatoms.

Examples of R ′ radicals containing heteroatoms are ethers, esters, amides, nitriles and heterocycles.

The radical R ′ is preferably a hydrocarbyl radical.

If R ′ is a hydrocarbyl radical, it may be substituted with heteroatoms or unsubstituted, preference is given to unsubstituted radicals.

The radical R ′ is preferably an aromatic hydrocarbyl radical.

Particularly preferred vinyl olefinically unsaturated monomers are vinyl aromatic hydrocarbons, especially vinyl toluene, alpha-methyl styrene and especially styrene.

When heteroatoms are present, olefinically unsaturated monomers are preferred, such as acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N, N-dimethylacrylamide, vinyl acetate, vinyl propionate, vinyl chloride, N-vinyl pyrrolidone, N-vinyl-caprolamide and N-vinyl-2-methylimidazoline.

Examples of suitable polyolefinically unsaturated monomers include esters of (meth) acrylic acid having an olefinic unsaturated radical R ″ and allyl ethers of mono- or polyhydric alcohols. The radical R ″ may be an allyl radical or a (meth) acrylic ester.

или

or

Preferred polyolefin unsaturated monomers include ethylene glycol di (meth) acrylate, 1,2-propylene glycol di (meth) acrylate, 1,3-propylene glycol di (meth) acrylate, butane-1,4-diol di (meth) acrylate, neopentyl glycol di ( meth) acrylate, 3-methylpentanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, hexanediol (meth) acrylate and allyl (meth) acrylate.

In addition, preferred polyolefinically unsaturated compounds include acrylic and methacrylic esters of alcohols having more than 2 OH groups, for example, trimethylolpropane tri (meth) acrylate or glyceryl tri (meth) acrylate, as well as trimethylolpropane di (meth) acrylate monoallyl simple ether, trimethylolpropane (meth) acrylate diallyl ether, pentaerythritol tri (meth) acrylate monoallyl ether, pentaerythritol di (meth) acrylate diallyl ether, pentaerythritol (meth) acrylate triallyl ether, triallyl saccharose and pentaallyl sucrose.

Particular preference is given to the use of allyl methacrylate.

A mixture of olefinically unsaturated monomers comprises at least one polyolefinically unsaturated monomer. The olefinically unsaturated monomer mixture preferably also includes one or more monounsaturated (meth) acrylic acid esters having an unsubstituted alkyl radical.

The mixture of olefinically unsaturated monomers preferably contains 0.1-6.0 mol%, more preferably 0.1-2.0 mol%, most preferably 0.1-1.0 mol%, of polyolefin unsaturated monomers.

The mixture of olefinically unsaturated monomers preferably contains 0.1-6.0 mol%, more preferably 0.1-2.0 mol%, most preferably 0.1-2.0 mol%, allyl methacrylate. More preferably, in addition to allyl methacrylate, additional polyolefinically unsaturated monomers are not present in the mixture.

The mixture of olefinically unsaturated monomers preferably contains <10.0 wt. %, more preferably <5.0 wt. % vinyl aromatic hydrocarbons, calculated on the total amount of olefinically unsaturated monomers. Most preferably, vinyl aromatic hydrocarbons are not present in the mixture of olefinically unsaturated monomers.

In a preferred embodiment, the olefinically unsaturated monomer mixture comprises:

- 98.0-99.5 wt. % of one or more monounsaturated esters of (meth) acrylic acid having unsubstituted alkyl radicals, where the alkyl radicals have a length of 1-10 carbon atoms, and

- 0.5-2.0 wt. % of one or more polyunsaturated esters of (meth) acrylic acid,

in each case, calculated on the total number of olefinically unsaturated monomers.

Preferably, at least one solvent is added to the mixture of olefinically unsaturated monomers, the solvent is miscible in any respect with water and in any respect with a mixture of olefinically unsaturated monomers. Particularly suitable solvents are N-methylpyrrolidone, N-ethylpyrrolidone and ethers alcohols, such as especially methoxypropanol.

As a result of the described production method, the copolymers in the inventive aqueous dispersion have a core / shell structure that can be achieved through a specific production process. This core / shell structure is characterized by a core comprising at least one polyurethane and a shell comprising at least a polymer that has been prepared by polymerization of olefinically unsaturated monomers.

The described core / shell structure is achieved through certain reaction conditions of accurately metered polymerization. Throughout the duration of the reaction, there are no large quantities of olefinically unsaturated monomers that can penetrate the polyurethane particles, in the presence of an initial polyurethane charge. Based on the constant presence of free radicals during monomer addition in the aqueous phase, which are provided with a water-soluble initiator, oligomers are immediately formed upon addition, which can no longer penetrate the polyurethane. Then they polymerize on the surface of the polyurethane.

In a preferred embodiment, the mass ratio of core to shell is 80: 20-20: 80, more preferably 60: 40-40: 60.

The microstructure of the copolymers can be investigated using transmission electron microscopy: for this purpose, it is necessary to include structures in the polymer that can be made counterposable, preferably by means of heavy metal compounds. This is preferably achieved during free radical copolymerization by incorporation of the polydiene sequences into the copolymer; copolymerization of isoprene or butadiene with olefinically unsaturated compounds and allyl compounds is preferred.

For analysis, a polymer film must be formed from the aqueous dispersion, which, after contrasting the atmosphere with osmium or ruthenium tetroxide enriched in the atmosphere, can be examined by electron microscopy.

The copolymers preferably have a particle size (z average) of 60-130 nm, more preferably 70-115 nm, measured by photocorrelation spectroscopy using Malvern Nano S90 (from Malvern Instruments) at 25 ± 1 ° C. A unit equipped with a 4 mW He-Ne laser at a wavelength of 633 nm covers a range of sizes from 1 to 3000 nm.

The copolymers may be crosslinked. The gel content of the invented aqueous dispersion is preferably 40-97 wt. %, more preferably 75-90 wt. %, in each case, calculated on solid particles in the dispersion.

The gel content can be determined gravimetrically, freeze-drying the dispersion, determining the total mass of the polymer dried by freezing, and then extracting the polymer in excess tetrahydrofuran (ratio of tetrahydrofuran to polymer dried by freezing = 300: 1) at 25 ° C for 24 hours. The insoluble fraction was removed and dried in an oven with air circulation at 50 ° C for 4 hours. After that, the dried insoluble fraction was weighed and this part was formed with the total weight of the freeze-dried polymer. The obtained value corresponds to the gel content.

The average molar mass of the copolymers is preferably 3 * 10 ⁷ g / mol - 8.5 * 10 ⁹ g / mol, the average molar mass was determined by scattering laser radiation at a small angle.

The acid number of the copolymers is 0-220 mg KOH / g solid resin, preferably 0-40 mg KOH / g solid resin, more preferably 0-25 mg KOH / g solid resin. The OH number is less than 70 and preferably less than 20 mg KOH / g of solid resin.

The acid number can be determined on the basis of DIN EN ISO 2114 in a homogeneous THF / water solution (9 vol. Parts THF and 1 vol. Part distilled water) with an ethanol solution of potassium hydroxide.

, R. Gnauck и R. Algeier, Plaste und Kautschuk, 20, 274 (1982), при помощи уксусного ангидрида в присутствии 4-диметиламинопиридина как катализатора в растворе тетрагидрофурана (THF)/диметилформамида (DMF) при комнатной температуре, с полным гидролизом оставшегося избытка уксусного ангидрида после ацетилирования и потециометрическим обратным титрованием уксусной кислоты спиртовым раствором гидроксида калия.The OH number can be determined based on R.-P.

, R. Gnauck and R. Algeier, Plaste und Kautschuk, 20, 274 (1982), using acetic anhydride in the presence of 4-dimethylaminopyridine as a catalyst in a solution of tetrahydrofuran (THF) / dimethylformamide (DMF) at room temperature, with the complete hydrolysis of the remaining excess acetic anhydride after acetylation and potentiometric reverse titration of acetic acid with an alcoholic solution of potassium hydroxide.

It is advantageous to apply the inventive dispersion to obtain coating materials, especially for basic coatings.

The present application also relates to a waterborne basecoat comprising the inventive dispersion.

A waterborne basecoat typically includes coloring pigments and / or optical effect pigments.

Lacke und Druckfarben [

Dictionary of Coating Materials and Printing Inks], Georg Thieme Verlag, Stuttgart, New York, 1998, стр. 176 и 451.Such coloring pigments and pigments for effect are described to a person skilled in the art, for example, in

Lacke und Druckfarben [

Dictionary of Coating Materials and Printing Inks], Georg Thieme Verlag, Stuttgart, New York, 1998, pp. 176 and 451.

Pigments for effect are, for example, pigments for a metallic effect, for example, aluminum pigments, gold bronze pigments, oxidized bronze pigments and / or aluminum oxide pigments of iron, pearlescent pigments, for example, pearlescent essence, basic lead carbonate, bismuth oxide chloride and / or metallic oxide mica pigments and / or other effect pigments, for example micronized titanium dioxide, plate graphite, plate iron oxide, multilayer effect pigments, composed of PVD films, and / or a liquid crystal polymer pigments.

The proportion of pigments is preferably in the range of 1.0-40.0 wt. %, preferably 2.0-20.0 wt. %, more preferably 5.0-15.0 wt. %, calculated on the total weight of the pigmented water-borne basecoat.

The inventive basecoat may include binders that are physically, thermally or thermally curable and with photochemical radiation.

In the context of the present invention, the term “physical cure” means the formation of a film by separation of solvents from polymer solutions or polymer dispersions. Usually, no crosslinking agents are needed for this purpose.

In the context of the present invention, the term "thermal cure" means the crosslinking of a layer of heat-initiated coating material in which either a crosslinking agent is present or the self-crosslinking binders are otherwise used in the base coating material. The crosslinking agent contains reactive functional groups that interact with reactive functional groups present in binders. It is usually referred to by experts as an external stapler. If additional reactive functional groups or auto-reactive functional groups, that is, groups that react with groups of the same kind, are already present in the molecules of the binder, then self-binding substances are present. Examples of suitable additional reactive functional groups and autoreactive functional groups are known from German Patent Application DE 19930665 A1, page 7 line 28 - page 9 line 24.

In the context of the present invention, photochemical radiation should be understood as electromagnetic radiation, such as near infrared (NIR), UV radiation, especially UV radiation, and particle radiation, such as electron beams. UV curing is usually initiated by free radical or cationic photoinitiators.

If thermal curing and curing with photochemical radiation are used together, respectively, "double curing" is also done.

In the present invention, preference is given to base coatings capable of curing thermally or thermally and with photochemical radiation, that is, by double curing.

Particularly preferred are base coatings that contain a polyurethane resin as a binder and an amine resin or a blocked or non-blocked polyisocyanate, preferably an amine resin, as a crosslinking agent. Along with amine resins, preference is given especially to melamine resins.

Preferably, a thixotropic additive is additionally present. Suitable thixotropic additives are inorganic thixotropic additives from the group of layered silicates. Especially suitable are lithium-aluminum-magnesium silicates.

Like inorganic thixotropic additives, however, one or more organic thixotropic additives can also be used. They are preferably selected from the group consisting of thixotropic additives of a (meth) acrylic acid (meth) acrylate copolymer, for example, the commercial product Viscalex HV30 (Ciba, BASF) and polyurethane thixotropic additives, for example, the commercial product DSX® 1550 from Cognis. Thixotropic additives of a copolymer of (meth) acrylic acid - (meth) acrylate are those which, like acrylic acid and / or methacrylic acid, also contain one or more acrylic esters (i.e. acrylates) and / or one or more methacrylic esters esters (i.e. methacrylates). A common feature of thixotropic additives of a copolymer of (meth) acrylic acid (meth) acrylate is that they exhibit a significant increase in viscosity in an alkaline medium, i.e. at pH> 7, especially> 7.5, through the formation of salts of acrylic acid and / or methacrylic acid, that is, through the formation of carboxylate groups. If (meth) acrylic esters are used which are formed from (meth) acrylic acid and C ₁ -C ₆ alkanol, then substantially non-associative thixotropic additives of a copolymer of (meth) acrylic acid - (meth) acrylate are obtained, for example, the aforementioned Viscalex HV30. Substantially non-associative thixotropic additives of a copolymer of (meth) acrylic acid - (meth) acrylate are also referred to in the literature as ASE thixotropic additives ("alkaline soluble / swellable emulsion additives"). However, thixotropic additives used for the (meth) acrylic acid - (meth) acrylate copolymer also include those called HASE thixotropic additives ("Hydrophobically Modified Anionic Soluble Emulsions"). They are obtained when the alkanols used, instead of or in addition to the C ₁ -C ₆ alkanols, are those that have a greater number of carbon atoms, for example, 7-30, or 8-20, carbon atoms. HASE thixotropic supplements have a significantly associated thixotropic effect. The thixotropic additives used for the (meth) acrylic acid - (meth) acrylate copolymer are unsuitable as binding resins due to their thixotropic properties; they are also not included among physically, thermally or thermally and photochemically curable binders, referred to as binders, and also clearly distinguishable from poly (meth) acrylate binders that can be used in the inventive base coat compositions. Polyurethane thixotropic additives should be understood as associative thixotropic additives referred to in the literature as HEUR ("Hydrophobically Modified Ethylene Oxide-Urethane Rheological Modifiers"). In chemical terms, they are non-ionic branched or unbranched block copolymers formed from chains of polyethylene oxide (sometimes also chains of polypropylene oxide) that are linked to each other via urethane bonds and which carry terminal long chain alkyl or alkylene groups having 8-30 carbon atoms. Typical alkyl groups are, for example, dodecyl or stearyl groups, the usual alkenyl group is, for example, the oleyl group, the usual aryl group is the phenyl group, and the usual alkylated aryl group is, for example, the nonylphenyl group. Due to their thixotropic properties and structure, polyurethane thixotropic additives are not suitable as physically, thermally or thermally and physically curable binder resins. They also clearly differ from polyurethanes, which can be used as binders in the inventive base coat compositions.

In addition, the waterborne basecoat may contain at least one additive. Examples of such additives are salts that are thermally decomposed without a residue or substantially without a residue, physically, thermally and / or photochemically radioactive curable resins, other than polyurethane resins as binders, additional crosslinking agents, organic solvents, reactive diluents, transparent pigments , fillers, dyes, soluble in molecular dispersion, nanoparticles, light stabilizers, antioxidants, deaerating agents, emulsifiers, lubricants, polymerization inhibitors free radical polymerization initiators, adhesion promoters, leveling additives, film-forming aids, sedimentation agents (SCAs), refractory additives, corrosion inhibitors, waxes, desiccants, biocides and matting agents.

Suitable additives of the above type are known, for example, from

- German patent application DE 19948004 A1, p. 14 line 4 - p. 17 line 5,

- German patent DE 10043405 C1, column 5, paragraphs [0031] to [0033].

They are used in conventional and known amounts.

The solids content of the applied basecoats in accordance with the invention may vary according to the requirements of each individual case. First of all, the solids content is dictated by the viscosity required for application, especially spray application, and thus, it can be adjusted by a person skilled in the art based on his general knowledge of a specialist, optionally with a few research tests.

The solids content of the base coat is preferably 5-70 wt. %, more preferably 10-65 wt. % and particularly preferably 15-60 wt. %

The solids content is understood to mean a mass proportion that remains as a residue upon evaporative concentration under fixed conditions. Particulate matter was determined according to DIN EN ISO 3251 at 130 ° C, 60 min, initial weight 1.0 g.

The applied basecoats in accordance with the invention can be obtained using mixing processes and mixing plants generally accepted and known for preparing basecoats.

The invented basecoats can be applied in the form of a single-component (1K), two-component (2K), or multi-component (3K, 4K) systems. Preference is given to (1K) systems.

In single component (1K) systems, the binder and the crosslinking agent are present together with each other, i.e. in one component. The premise for this is that these two components stitch together only at relatively high temperatures and / or when exposed to actinic radiation.

In bicomponent (2K) systems, for example, a binder and a crosslinking agent are present separately in at least two components that are only quickly connected before application. This form is chosen when the binder and the crosslinking agent already react with each other at room temperature. Coatings of this type are especially used for coating thermally sensitive substrates, especially in auto-mechanical refinishing.

The pigmented water-borne basecoat used in accordance with the invention can be applied to the base with conventional layer thicknesses within the automotive industry, in the range from, for example, 5 to 100 micrometers, preferably 5-60 micrometers (layer thickness after the drying operation). This includes the application, for example, of known methods, such as spraying, coating with the removal of excess using a strip, painting, pouring, coating by immersion, impregnation, irrigation or coating with a roller. Preference is given to using spray methods, such as compressed air spray, non-compressor spray, high speed rotation, electrostatic spray (ESTA), optionally combined with a hot spray application, for example, hot compressed air spray.

After the pigmented water-borne base coat has been applied, it can be dried by known methods. For example, (1K) basecoats can be vaporized at room temperature for 1 to 60 minutes, and further preferably dried at, optionally, slightly elevated temperatures from 30 to 80 ° C. Evaporation and drying, as is understood in the context of the present invention, means the evaporation of organic solvents and / or water, as a result of which the coating material becomes drier, but does not harden, or a film of a still not completely crosslinked coating material is formed.

A standard commercial self-healing coating is then applied in a similar manner to standard methods, the dry layer thickness is again within standard ranges, for example, 5-100 micrometers. Such self-healing coatings are known to those skilled in the art.

After applying a self-healing coating, it can be vaporized at room temperature, for example, for 1 to 60 minutes, and optionally dried. Then, the self-healing coating is cured with the pigmented base coat applied. In the course of this, crosslinking reactions can occur, for example, which produce the inventive multilayer color and / or effect based ink system. Curing is preferably carried out thermally or thermally with actinic radiation at temperatures of 20-200 ° C.

An additional object of the present invention is a method for producing a multilayer color and / or for the effect of a colorful system, in which

(a) a pigmented water-borne basecoat is applied to the base,

(b) form a polymer film from a coating material deposited in stage (a),

(c) applying a self-healing coating to the base coat layer thus obtained, and then

(d) the base coat layer is cured together with the self-healing coating layer,

which includes the use in step (a) of a pigmented water-borne basecoat, wherein said basecoat includes the inventive dispersion.

All the details given above with respect to the inventive dispersion and water-borne basecoat also apply to the inventive use and to the method according to the invention. This is also particularly applicable to all preferred, particularly preferred and very particularly preferred features.

Advantageously, the inventive water-borne basecoat can be used to coat car bodies and / or plastic parts for installation in car bodies.

Using the method according to the invention, it is possible to paint metallic and non-metallic substrates, especially plastic substrates, preferably automobile bodies or parts thereof.

The invention is further illustrated by way of examples.

Examples

, R. Gnauck и R. Algeier, Plaste und Kautschuk, 20, 274 (1982), с помощью уксусного ангидрида в присутствии 4-диметиламинопиридина в качестве катализатора в растворе тетрагидрофуран (ТНР)/диметилформамид (DMF) при комнатной температуре, с полным гидролизом оставшегося избытка уксусного ангидрида после ацетилирования и потециометрическим обратным титрованием уксусной кислоты спиртовым раствором гидроксида калия. Время ацетилирования 60 мин было достаточным во всех случаях, чтобы обеспечить полное превращение.Unless otherwise indicated, the hydroxyl number in the examples that follow was determined based on R.-P.

, R. Gnauck and R. Algeier, Plaste und Kautschuk, 20, 274 (1982), using acetic anhydride in the presence of 4-dimethylaminopyridine as a catalyst in a solution of tetrahydrofuran (THP) / dimethylformamide (DMF) at room temperature, with complete hydrolysis the remaining excess of acetic anhydride after acetylation and potentiometric reverse titration of acetic acid with an alcohol solution of potassium hydroxide. Acetylation time of 60 minutes was sufficient in all cases to ensure complete conversion.

Unless otherwise indicated, the acid number in the examples that follow was determined based on DIN EN ISO 2114 in a homogeneous THF / water solution (9 vol. Parts THF and 1 vol. Part distilled water) with an ethanol solution of potassium hydroxide.

Unless otherwise indicated, the solids content, also referred to herein as solid particles, was determined in the examples that follow, according to DIN EN ISO 3251 at 130 °; 60 min, initial weight 1.0 g.

, G.

, K.-F. Arndt, "Leitfaden der Polymercharakterisierung" [Guidelines for Polymer Characterization], Akademie-Verlag, Berlin, стр. 47-54, 1982.The number average molar mass (M _n ) in the examples that follow, unless otherwise indicated, was determined using a 10.00 vapor phase osmometer (from Knauer) on concentration series in toluene at 50 ° C. according to E.

, G.

, K.-F. Arndt, "Leitfaden der Polymercharakterisierung" [Guidelines for Polymer Characterization], Akademie-Verlag, Berlin, pp. 47-54, 1982.

Polyurethane dispersions

Example D-P1

Obtaining a dispersion of unsaturated polyesteruritan having alpha-methylstyryl groups

Polyurethans (В)" [Получение изобретенного полиуретана (В)], за исключением того, что твердые частицы в полученной дисперсии составили только 29% амин 35 мас. %. В пересчете на аддукт (В2), упомянутый в описании патента DE 19948004 В4, пример получения 1, аддукт получили из моноэтаноламина и триметилолпропана вместо диэтаноламина:The dispersion of alpha-methylstyryl-containing polyurethane was obtained based on the description of patent DE 19948004 B4, page 27, example 1, "Herstellung eines

Polyurethans (B) "[Obtaining the invented polyurethane (B)], except that the solids in the resulting dispersion were only 29% amine 35 wt.%. In terms of adduct (B2) mentioned in the description of patent DE 19948004 B4, production example 1, the adduct was obtained from monoethanolamine and trimethylolpropane instead of diethanolamine:

For this purpose, a reaction vessel equipped with a stirrer, an internal thermometer, a reflux condenser and an electric heater was first charged with a nitrogen atmosphere of 200.0 wt. parts of methyl ethyl ketone, 800.0 wt. parts of N-methylpyrrolidone and 221.3 wt. parts of monoethanolamine (from BASF SE) at 20 ° C. 778.7 wt.% Were added dropwise to this mixture over an hour and a half. parts of 1- (1-isocyanato-1-methylethyl) -3- (1-methylethynyl) benzene (TMI® (META) Unsaturated Aliphatic Isocyanate, from Cytec), having an isocyanate content of 20.4 wt. % isocyanate, so that the reaction temperature did not exceed 40 ° C. The resulting reaction mixture was stirred until no more free isocyanate groups could be detected. After that, the reaction mixture was stabilized 200 ppm. hydroquinone.

The theoretical solids content of the thus obtained solution of the described adduct was 50 wt. %

Then, in an additional reaction vessel equipped with a stirrer, an internal thermometer, a reflux condenser and an electric heater, 431.7 wt. parts of linear polyester polyol and 69.7 wt. parts of dimethylolpropionic acid (from GEO Specialty Chemicals) was dissolved in 355.8 wt. parts of methyl ethyl ketone and 61.6 wt. parts of N-methylpyrrolidone in a nitrogen atmosphere. Linear polyester polyol was obtained in advance from the dimerized fatty acid (Pripol ^® 1012 from Uniqema), izoftalovoy acid (from BP Chemicals) and hexane-1,6-diol (from BASF SE) (weight ratio of the starting materials: dimer fatty acid to izoftalovoy acid to hexane-1,6-diol = 54.00: 30.02: 15.98) and has a hydroxyl number of 73 mg KOH / g of solid particles and a number average molar mass of 1379 g / mol.

To the resulting solution was added at 45 ° C, 288.6 wt. parts of isophorone diisocyanate (Basonat® I, from BASF SE) having an isocyanate content of 37.75 wt. % After the exothermic reaction ceased, the reaction mixture was gradually heated to 80 ° C, while stirring. Stirring at this temperature continued until the solution isocyanate content was 3.2 wt. % and it was not so constantly. After that, the reaction mixture was cooled to 65 ° C, and 85.2 wt. parts of the above adduct together with 21.8 wt. parts of trimethylolpropane (from BASF SE). The resulting reaction mixture was stirred at 65 ° C until the solution isocyanate content dropped to 1.0 wt. % Now added 22.2 wt. % diethanolamine (from BASF SE) and the content of isocyanate groups were monitored until free isocyanate groups could no longer be detected. The resulting diluted polyurethane was mixed with 139.7 wt. parts of methoxypropanol and 43.3 wt. parts of triethylamine (from BASF SE). 30 minutes after the addition of the amine, the temperature of the solution was lowered to 60 ° C, and then 1981 wt. parts of deionized water, while stirring for 30 minutes. Methyl ethyl ketone was distilled off from the resulting dispersion at 60 ° C. under reduced pressure. After that, any loss of solvent and water was made up.

The dispersion of alpha-methylstyryl-containing polyurethane, thus obtained, had a solids content of 29.0 wt. %; the acid number was 34.0 mg KOH / g solids content and the pH was 7.0 (measured at 23 ° C).

D-P2 Example

Obtaining a dispersion of saturated polyesterurethane having isotridecyl groups

A polyurethane dispersion was prepared as in comparative example DP-1, except that it did not have alpha-methylstyrene groups, but had isotridecyl groups.

In a reaction vessel equipped with a stirrer, an internal thermometer, a reflux condenser and an electric heater, 440.1 wt. parts of the linear polyester polyol prepared from a dimerized fatty acid (Pripol ^® 1012 from Uniqema), isophthalic acid (from BP Chemicals) and hexane-1,6-diol (BASF SE) (weight ratio of the starting materials: dimer fatty acid to isophthalic acid to hexane-1,6-diol = 54.00: 30.02: 15.98), having a hydroxyl number of 73 mg KOH / g of solid particles and a number average molar mass of 1379 g / mol, as well as 71.1 wt. parts of dimethylolpropionic acid (from GEO Specialty Chemicals), dissolved in 362.7 wt. parts of methyl ethyl ketone and 62.8 wt. parts of N-methylpyrrolidone in a nitrogen atmosphere. To the solution obtained as a result, at 45 ° C, 294.3 wt. parts of isophorone diisocyanate (Basonat® I, from BASF SE) having an isocyanate content of 37.75 wt. % After the exothermic reaction ceased, the reaction mixture was gradually heated to 80 ° C, while stirring. Stirring was continued at this temperature until the solution isocyanate content was 3.2 wt. % and was constant. After that, the reaction mixture was cooled to 70 ° C, and 33.1 wt. parts of isotridecyl alcohol (Isotridecanol N, from BASF SE) together with 19.3 wt. parts of trimethylolpropane (from BASF SE) and 25.6 wt. parts of methyl ethyl ketone. The resulting reaction mixture was stirred at 70 ° C until the solution isocyanate content dropped to 0.8 wt. % At this moment, 19.6 wt. % diethanolamine (from BASF SE) and the content of isocyanate groups was measured until no more free isocyanate groups could be detected. The resulting diluted polyurethane was mixed with 123 wt. parts of methoxypropanol and 43.8 wt. parts of triethylamine (from BASF SE). 30 minutes after the addition of the amine, the temperature of the solution was lowered to 60 ° C, and then, after 30 minutes, 2009 wt. parts of deionized water while stirring. Methyl ethyl ketone was distilled off from the resulting dispersion at 60 ° C. under reduced pressure. After that, any loss of solvent and water was made up.

The polyurethane dispersion thus obtained had a solids content of 29.0 wt. %; the acid number was 34.1 mg KOH / g solids content and the pH was 7.0 (measured at 23 ° C).

Example D-P3

Obtaining a dispersion of saturated polyetherurethane with polytetramethylene oxide segments

To a reaction vessel equipped with a stirrer, an internal thermometer, a reflux condenser and an electric heater, 685.8 wt. parts of linear alpha, with an omega-hydroxy terminus of polytetramethylene oxide (PolyTHF ^® 2000, from BASF SE) having a hydroxyl number of 56.1 mg KOH / g of solid particles and an average molecular weight of 2000 g / mol, 138.0 wt. parts of dimethylolpropionic acid (from GEO Specialty Chemicals), 0.01 wt. parts of dibutyltin dilaurate and 685.8 wt. parts of methyl ethyl ketone was dissolved in nitrogen atmosphere at 70 ° C. To the resulting solution was added 418.8 wt. parts of m-tetramethylxylene diisocyanate (TMXDI® (Meta) Aliphatic Isocyanate, from Cytec) having an isocyanate content of 34.4 wt. % Then, the reaction mixture was gradually heated to 80 ° C, while stirring, and kept at this temperature until the solution isocyanate content was 1.8 wt. % and it was not so constantly. After that, 87.4 wt. parts of trimethylolpropane (from BASF SE) and 26.1 wt. parts of methyl ethyl ketone were quickly added to the reaction mixture. The resulting reaction mixture was stirred at 80 ° C until free isocyanate groups could no longer be detected. The resulting diluted polyurethane was mixed with 41.2 wt. parts of dimethylethanolamine and stirred for an additional 60 minutes. After that, the reaction mixture was completely transferred, while constantly stirring for a period of 30 minutes, into the second reaction vessel, which was already initially loaded 1732 wt. parts of deionized water, which was previously heated to 70 ° C. Methyl ethyl ketone was distilled off from the resulting dispersion at 60 ° C. under reduced pressure. After that, any loss of water was made up for.

The polyurethane dispersion thus obtained had a solids content of 38.0 wt. %; the acid number was 43.0 mg KOH / g of solids and the pH was 6.2 (measured at 23 ° C).

Example D-P4

Obtaining a known dispersion of sulfur-containing saturated polyesterurethane

Polyurethans und einer

Dispersion hiervon" [Получение изобретенного полиуретана и его водной дисперсии], нейтрализовали триэтиламином и затем преобразовали в водную дисперсию полиуретана. Метилэтилкетон отгоняли из полученной дисперсии при 60°С под сниженным давлением. После этого, любые потери воды восполняли.According to EP 1330480 B1, the polyester polyol according to Production Example 1, p. 15, was used to obtain a polyurethane prepolymer according to Production Example 2, p. 15, which reacted with thioethanol according to Example 1, p. 16 "Die Herstellung eines

Polyurethans und einer

Dispersion hiervon "[Preparation of the invented polyurethane and its aqueous dispersion] was neutralized with triethylamine and then converted to an aqueous dispersion of polyurethane. Methyl ethyl ketone was distilled off from the resulting dispersion at 60 ° C. under reduced pressure. After that, any water loss was made up for.

The dispersion of sulfur-containing polyurethane obtained in this way had a solids content of 27.3 wt. %; the acid number was 34.4 mg KOH / g of solids content, the neutralization level was 84% and the pH was 7.1 (measured at 23 ° C).

Dispersion of a polyurethane-polyacrylate copolymer

Example D-A1

Obtaining the original dispersion of a copolymer of polyesterurethane-polyacrylate derived from unsaturated polyesterurethane having alpha-methylstyryl groups

eines

Mischpolymerisats 1" [Получение исходной дисперсии изобретенного сополимера 1], и описания патента ЕР 1218434 В1, стр. 24, пример 2, "Die Herstellung der

eines

Pfropfmischpolymerisats 1" в атмосфере азота, 1937.8 мас. частей дисперсии полиуретана согласно примеру DP-1 разбавили 856.9 мас. частями деионизированной воды и нагревали до 85°С. При этой температуре, при стандартном давлении, смесь 160.7 мас. частей стирола, 160.7 мас. частей метилметакрилата, 120.3 мас. частей н-бутилакрилата и 120.3 мас. частей гидроксиэтилметакрилата равномерно добавляли к дисперсии, перемешивая при этом в течение 3.5 часов. С начала добавления смеси мономеров, в пределах 4 часов добавляли раствор 8.4 мас. частей трет-бутил пероксиэтилгексаноата в 134.9 мас. частях метоксипропанола. Полученную в результате реакционную смесь перемешивали при 85°С до тех пор, пока все мономеры прореагировали (общее содержание мономеров (ГХ) относительно дисперсии <0.1%).Based on the description of patent DE 19948004 B4, page 27, example 2, "Die Herstellung der

eines

Mischpolymerisats 1 "[Preparation of the original dispersion of the invented copolymer 1], and patent specification EP 1218434 B1, p. 24, example 2," Die Herstellung der

eines

Pfropfmischpolymerisats 1 "in a nitrogen atmosphere, 1937.8 parts by weight of a polyurethane dispersion according to Example DP-1 was diluted with 856.9 parts by weight of deionized water and heated to 85 ° C. At this temperature, at standard pressure, a mixture of 160.7 parts by weight of styrene, 160.7 parts by weight. parts of methyl methacrylate, 120.3 parts by weight of n-butyl acrylate and 120.3 parts by weight of hydroxyethyl methacrylate were uniformly added to the dispersion while stirring for 3.5 hours. From the beginning of the addition of the monomer mixture, a solution of 8.4 parts by weight of tert-butyl peroxyethyl hexanoate was added over 4 hours. 134.9 m parts of methoxypropanol The resulting reaction mixture was stirred at 85 ° C until all monomers reacted (total monomer content (GC) relative to the dispersion <0.1%).

During free radical polymerization, at intervals of 30 minutes, the content of free monomers was determined by gas chromatography (GC) (GC: 50 m capillary column with silica with a phase of polyethylene glycol or 50 m capillary column with silica with a phase of polydimethylsiloxane, a helium carrier gas , injector for injection of samples with a flow division of 150 ° C, thermostat temperature range of 40-220 ° C, flame ionization detector, detector temperature of 275 ° C, internal standard isobutyl acrylate), and the highest monomere content s relative to the dispersion was determined after 30 min with 1.8 wt. % (11.1 wt.% Based on vinyl monomer).

The obtained initial dispersion of the copolymer had, as described in the primary example, very good storage stability. The solids content in it was 32.5 wt. %, the acid number was 18.3 mg KOH / g solids content and its pH was 7.2 (measured at 23 ° C). Particle size (z averaging) using photocorrelation spectroscopy was 104 nm. Using gas chromatography (GC: 50 m capillary column with silica with a phase of polyethylene glycol or 50 m capillary column with silica with a phase of polydimethylsiloxane, a carrier gas helium, an injector for introducing samples with a flow division of 250 ° C, the temperature of the thermostat 40- 220 ° C, flame ionization detector, detector temperature 275 ° C, internal standard n-propyl glycol), the content of 6.0 wt. % methoxypropanol and 1.7 wt. % n-methylpyrrolidone.

After extraction with tetrahydrofuran of the freeze-dried polymer, the gel content, determined gravimetrically, was 71.5 wt. % For this purpose, the dispersion was freeze dried, the mass of the freeze dried polymer was determined, then the polymer was extracted at 25 ° C in excess tetrahydrofuran (ratio of tetrahydrofuran to freeze dried copolymer = 300: 1) for 24 hours. The insoluble content (gel content) was isolated, dried at 50 ° C in an oven with air circulation for 4 hours, and then weighed again.

Example D-A2

Obtaining the initial dispersion of a polyester urethane-polyacrylate copolymer derived from saturated polyester urethane having isotridecyl groups

Analogously to the preparation example D-A1, the primary dispersion was obtained by replacing the dispersion of a polyurethane having alpha-methylstyryl groups, according to the production example of D-P1 for the same mass of the dispersion of a polyurethane having isotridecyl groups obtained according to the preparation example of D-P2.

During free radical polymerization, at intervals of 30 minutes, the content of free monomers was determined by gas chromatography as in Example D-A1, and the highest total content of monomers in terms of dispersion was determined after 30 minutes, which should be 2.0 wt. % (12.4 wt.% In terms of vinyl monomer).

The resulting primary copolymer dispersion has very good storage stability. Its solids content was 32.2 wt. %, the acid number was 18.1 mg KOH / g solids content and the pH was 7.3 (measured at 23 ° C). The particle size (z average) measured by photocorrelation spectroscopy was 112 nm. Analogously to example D-A1, by gas chromatography, the content of 5.7 wt. % methoxypropanol and 1.2 wt. % N-methylpyrrolidone.

Analogously to example D-A1, the gel content, determined gravimetrically after extraction with tetrahydrofuran, was 70.2 wt. % Example D-A3

Obtaining the initial dispersion of a polyesterurethane-polyacrylate copolymer (isoprene comonomer) derived from an unsaturated polyesterurethane having alpha-methylstyryl groups

As in the preparation example of D-A1, a primary dispersion of the copolymer was obtained, except that 15 mol% of vinyl monomers were changed to isoprene: thus, 1937.8 wt. parts of a dispersion of polyurethane according to an example of obtaining D-P1 was diluted 857.0 wt. parts of deionized water and heated to 85 ° C. At this temperature, the mixture is 145.2 wt. parts of styrene, 145.2 wt. parts of methyl methacrylate, 108.7 wt. parts of n-butyl acrylate, 108.7 wt. parts of hydroxyethyl methacrylate and 54.3 wt. parts of isoprene was uniformly added to the dispersion, while stirring under a calibration pressure of nitrogen of 3 bar throughout the course of 3.5 hours. With the start of adding the monomer mixture, a solution of 8.4 wt. parts of tert-butyl peroxyethyl hexanoate in 134.9 wt. parts of methoxypropanol. The resulting reaction mixture was further stirred at 85 ° C until all monomers had reacted.

The resulting primary dispersion has very good storage stability. Its solids content was 32.3 wt. %, the acid number was 18.3 mg KOH / g and the pH was 7.2 (measured at 23 ° C). The particle size (z average) measured by photocorrelation spectroscopy was 115 nm. Analogously to example D-A1, by gas chromatography, the content of 6.0 wt. % methoxypropanol and 1.7 wt. % N-methylpyrrolidone.

Analogously to example D-A1, the gel content, determined gravimetrically after extraction with tetrahydrofuran, was 70.8 wt. %

Example D-A4

Obtaining an initial dispersion of a polyester urethane-polyacrylate copolymer (without styrene comonomer) derived from an unsaturated polyester urethane having alpha-methyl styryl groups

As in the preparation example of D-A1, a primary dispersion of the copolymer was obtained, except that the proportion of styrene was replaced with the same mass of methyl methacrylate and the solids content was reduced to 28%:

Thus, in an atmosphere of nitrogen, 1689.6 wt. parts of a dispersion of polyurethane was diluted 1133.5 wt. parts of deionized water and 142.4 wt. parts of N-methylpyrrolidone, and heated to 85 ° C. At this temperature, at standard pressure, a mixture of 280.3 wt. parts of methyl methacrylate, 104.9 wt. parts of n-butyl acrylate and 104.9 wt. parts of hydroxyethyl methacrylate was uniformly added to the dispersion, while stirring for the entire course of 3.5 hours. With the start of adding the monomer mixture, a solution of 7.4 wt. parts of tert-butyl peroxyethyl hexanoate in 37.0 wt. parts of methoxypropanol. The resulting reaction mixture was further stirred at 85 ° C until all monomers had reacted.

During free radical polymerization, at intervals of 30 minutes, the content of free monomers was determined analogously to example D-A1 by gas chromatography, and the highest total content of monomers in terms of dispersion was determined after 30 minutes, which should be 1.0 wt. % (7.1 wt.% In terms of vinyl monomer).

The resulting primary dispersion of the copolymer, as well as the styrene-containing dispersion, had very good storage stability. Its solids content was adjusted to 28.0 wt. %; the acid number was 18.1 mg KOH / g solids and the pH was 7.2 (measured at 23 ° C). The particle size (z average) measured by photocorrelation spectroscopy was 102 nm. Analogously to example D-A1, by gas chromatography, the content of 2.8 wt. % methoxypropanol and 5.8 wt. % N-methylpyrrolidone. Analogously to example D-A1, the gel content, determined gravimetrically after extraction with tetrahydrofuran, was 72.0 wt. % Example D-A5

Obtaining an initial dispersion of a polyester urethane-polyacrylate copolymer derived from saturated, sulfur-containing polyester urethane (without solvents)

eines

Polymergemischs" [Получение исходной дисперсии изобретенной полимерной смеси], 2285.8 мас. частей дисперсии полиуретана согласно примеру DP-4 первоначально загружали в атмосфере азота и нагревали до 82°С. При этой температуре, при стандартном давлении, смесь 118.8 мас. частей стирола, 207.7 мас. частей гидроксипропил метакрилата, 59.8 мас. частей н-бутил акрилата, 88.9 мас. частей метил метакрилата и 118.8 мас. частей трет-бутилциклогексил акрилата равномерно добавляли к дисперсии, перемешивая при этом на протяжении всего курса 4 часов. С началом добавления смеси мономера, на протяжении 4.5 часов добавляли 29.9 мас. частей трет-бутил пероксиэтилгексаноата. После окончания подачи инициатора, полимеризацию продолжали при 82°С на протяжении одного часа. Во время свободнорадикальной полимеризации, при интервалах 30 минут, содержание свободных мономеров определяли аналогично примеру D-A1 путем газовой хроматографии, и самое высокое общее содержание мономеров определяли после 30 мин, которое должно составлять 1.6 мас. % в пересчете на 41.9 мас. % дисперсии (7.6 мас. % в пересчете на виниловый мономер).According to EP 1,330,480 B1, Example 2, p. 16, "Die Herstellung der

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Polymergemischs "[Preparation of the original dispersion of the invented polymer mixture], 2285.8 parts by weight of the dispersion of the polyurethane according to Example DP-4 was initially charged under nitrogen and heated to 82 ° C. At this temperature, at standard pressure, a mixture of 118.8 parts by weight of styrene, 207.7 parts by weight of hydroxypropyl methacrylate, 59.8 parts by weight of n-butyl acrylate, 88.9 parts by weight of methyl methacrylate and 118.8 parts by weight of tert-butylcyclohexyl acrylate were uniformly added to the dispersion while stirring for 4 hours. numbers, 29.9 parts by weight of tert-butyl peroxyethyl hexanoate was added over 4.5 hours. After the initiator was fed, polymerization was continued at 82 ° C. for one hour. During free radical polymerization, at 30 minute intervals, the content of free monomers was determined analogously to Example D- A1 by gas chromatography, and the highest total monomer content was determined after 30 min, which should be 1.6 wt. % in terms of 41.9 wt. % dispersion (7.6 wt.% in terms of vinyl monomer).

The resulting primary dispersion was also diluted with 590.3 wt. parts of water, so as to obtain a solids content as in EP 1330480 B1, example 2, 34.8 wt. %

The acid number was 19.6 mg KOH / g solids content and the pH of the dispersion was 7.4 (measured at 23 ° C). The level of neutralization was 80.2%. The particle size (z average) measured by photocorrelation spectroscopy was 83 nm. The resulting dispersion does not contain a solvent.

Similarly to example D-A1, the gel content, determined gravimetrically after extraction with tetrahydrofuran, was 0.0 wt. %

Example D-A6

Obtaining the initial dispersion of a polyesterurethane-polyacrylate copolymer, derived from saturated, sulfur-containing polyesterurethane, and the addition of methoxypropanol and N-methylpyrrolidone

Analogously to example D-A5, a copolymer was obtained.

The resulting primary dispersion having a solids content of 41.9 wt. %, after the end of the continued polymerization, 77.0 wt. parts of methoxypropanol, 206.5 wt. parts of N-methylpyrrolidone and 306.8 wt. parts of water, so as to result in a solids content of 34.8 wt. %, similar to comparative example D-A5.

The acid number was 18.5 mg KOH / g solids content and the pH was 7.2 (measured at 23 ° C). The level of neutralization was 80.0%. Particle size (z average) measured by photocorrelation spectroscopy was 81 nm. By gas chromatography, analogously to example D-A1, the content of 2.2 wt. % methoxypropanol and 5.9 wt. % N-methylpyrrolidone. As in Example D-A5, it was not possible to determine any gel content (gel content = 0.0 wt.%).

Example D-B1

Obtaining the invented starting dispersion of a polyester urethane-polyacrylate copolymer derived from an unsaturated polyester urethane having alpha-methyl styryl groups

To obtain the initial dispersion of the invented copolymer, in an atmosphere of nitrogen, 1961.2 wt. parts of a dispersion of alpha-methylstyryl-containing polyurethane according to an example of obtaining D-P1 was diluted with 40.0 wt. parts of methoxypropanol (0.07% in terms of polyurethane) and 686.5 wt. parts of deionized water, and heated to 80 ° C. After the content of the reactor was heated to 80 ° C, 0.6 wt. parts of ammonium peroxodisulfate were dissolved in 35.7 wt. parts of deionized water and added to the reactor at standard pressure. Further, while constantly stirring, a mixture of 301.6 wt. parts of methyl methacrylate, 261.6 wt. parts of n-butyl acrylate, 5.6 wt. parts of allyl methacrylate (0.87 mol%, calculated on the total vinyl monomer) and 134.9 wt. parts of N-methylpyrrolidone was uniformly added throughout the course of 5 hours. With the start of adding a mixture of monomer, a solution of 1.1 wt. parts of ammonium peroxodisulfate in 71.3 wt. parts of deionized water were likewise added over five hours.

During free radical polymerization, at intervals of 30 minutes, the content of free monomers was determined analogously to example D-A1 by gas chromatography, and the highest total content of monomers in terms of dispersion was determined after 30 minutes, which should be 0.5 wt. % (3.1 wt.% In terms of vinyl monomer).

After the dosed addition of monomer and initiator was completed simultaneously, the resulting reaction mixture was stirred at 80 ° C for an additional hour and then cooled to room temperature.

The resulting primary copolymer dispersion has very good storage stability. Its solids content was 32.5%, the acid number was 18.8 mg KOH / g solids content and the pH was 7.0. Particle size (z average) measured by photocorrelation spectroscopy was 96 nm. Analogously to example D-A1, by gas chromatography, the content of 2.7 wt. % methoxypropanol and 5.7 wt. % N-methylpyrrolidone.

Analogously to example D-A1, the gel content, determined gravimetrically after extraction with tetrahydrofuran, was 80.3 wt. %

Example D-B2

Obtaining the invented starting dispersion of a polyester urethane-polyacrylate copolymer derived from a saturated polyester urethane having isotridecyl groups

Similarly to the production example of D-B1, the primary dispersion was obtained by replacing a dispersion of a polyurethane having alpha-methylstyryl groups according to the production example of D-P1 for the same mass of a dispersion of a polyurethane having isotridecyl groups according to the production example of D-P2. During free radical polymerization, at intervals of 30 minutes, the content of free monomers was determined analogously to example D-A1 by gas chromatography, and the highest total content of monomers in terms of dispersion was determined after 30 minutes, which should be 0.5 wt. % (3.1 wt.% In terms of vinyl monomer).

The resulting primary copolymer dispersion had very good storage stability. Its solids content was 32.4 wt. %, the acid number was 18.4 mg KOH / g solids content and the pH was 6.9 (measured at 23 ° C). The particle size (z average) measured by photocorrelation spectroscopy was 102 nm. Analogously to example D-A1, by gas chromatography, the content of 2.4 wt. % methoxypropanol and 5.1 wt. % N-methylpyrrolidone.

Analogously to example D-A1, the gel content, determined gravimetrically after extraction with tetrahydrofuran, was 79.1 wt. %

Example D-B3

Obtaining the invented starting dispersion of a polyester urethane-polyacrylate copolymer (isoprene comonomer) derived from an unsaturated polyester urethane having alpha-methyl styryl groups

As in the production example of D-B1, in accordance with the invention, a primary dispersion of the copolymer was obtained, except that 15 mol% of vinyl monomers were changed to isoprene: thus, 1961.2 wt. parts of a dispersion of alpha-methylstyryl-containing polyurethane according to an example of obtaining D-P1 was diluted with 40.0 wt. parts of methoxypropanol and 686.5 wt. parts of deionized water, and heated to 80 ° C. At 80 ° C, 0.6 wt. parts of ammonium peroxodisulfate dissolved in 35.7 wt. parts of deionized water were added to the reactor under a 3 bar nitrogen calibration pressure. Further, maintaining pressure and constantly mixing, a mixture of 271.8 wt. parts of methyl methacrylate, 235.7 wt. parts of n-butyl acrylate, 5.9 wt. parts of allyl methacrylate (0.87 mol%, calculated on the total vinyl monomer) 55.3 wt. parts of isoprene and 134.9 wt. parts of N-methylpyrrolidone was uniformly added throughout the course of six hours. With the start of adding a mixture of monomer, a solution of 1.1 wt. parts of ammonium peroxodisulfate in 71.3 wt. portions of deionized water were also added over six hours. After the dosed addition of monomer and initiator was completed simultaneously, the resulting reaction mixture was stirred at 80 ° C for an additional hour and then cooled to room temperature.

The resulting primary dispersion of the grafted copolymer has very good storage stability. Its solids content was 32.2 wt. %, acid number 18.8 mg KOH / g solids content and pH was 7.0 (measured at 23 ° C). Particle size (z average) measured by photocorrelation spectroscopy was 97 nm. Analogously to example D-A1, by gas chromatography, the content of 2.8 wt. % methoxypropanol and 5.6 wt. % N-methylpyrrolidone.

Analogously to example D-A1, the gel content, determined gravimetrically after extraction with tetrahydrofuran, was 78.0 wt. %

Example D-B4

Obtaining the invented starting dispersion of a polyester urethane-polyacrylate copolymer derived from an unsaturated polyester urethane having alpha-methyl styryl groups

To obtain the initial dispersion of the invented copolymer, in a nitrogen atmosphere, 1689.7 wt. parts of a dispersion of alpha-methylstyryl-containing polyurethane according to an example of obtaining D-P1 was diluted with 40.3 wt. parts of methoxypropanol (0.08% in terms of polyurethane) and 993.8 wt. parts of deionized water, and heated to 80 ° C. Once the content of the reactor was heated to 80 ° C, 0.7 wt. parts of ammonium peroxodisulfate dissolved in 46.1 wt. parts of deionized water were added to the reactor at standard pressure. Further, while constantly mixing, according to an example of obtaining D-A4, a mixture of 277.6 wt. parts of methyl methacrylate, 103.8 wt. parts of n-butyl acrylate and 103.8 wt. parts of hydroxyethyl methacrylate, and an additional 4.8 wt. parts of allyl methacrylate (0.86 mol% in terms of total vinyl monomer) together with 145.7 wt. parts of N-methylpyrrolidone were uniformly added throughout the course of five hours. With the start of adding a monomer mixture, a solution of 1.5 wt. parts of ammonium peroxodisulfate in 92.2 wt. parts of deionized water were likewise added over five hours.

During free radical polymerization, at intervals of 30 minutes, the content of free monomers was determined analogously to example D-A1 by gas chromatography, and the highest total content of monomers in terms of dispersion was determined after 30 minutes, which should be 0.5 wt. % (3.6 wt.% In terms of vinyl monomer).

After the dosed addition of monomer and initiator was completed simultaneously, the resulting reaction mixture was stirred at 80 ° C for an additional hour and then cooled to room temperature.

The resulting primary copolymer dispersion has very good snoring stability. Its solids content was 28.0 wt. %, the acid number was 18.2 mg KOH / g solids content and the pH was 7.0. The particle size (z average) measured by photocorrelation spectroscopy was 110 nm. Analogously to example D-A1, by gas chromatography, the content of 2.9 wt. % methoxypropanol and 5.9 wt. % N-methylpyrrolidone. Analogously to example D-A1, the gel content, determined gravimetrically after extraction with tetrahydrofuran, was 81.2 wt. %

Example D-B5

Obtaining the invented starting dispersion of a polyester urethane-polyacrylate copolymer derived from saturated, sulfur-containing polyester urethane (diluted with a solvent)

To obtain the initial dispersion of the invented copolymer, in a nitrogen atmosphere, 2101.9 wt. parts of a dispersion of polyurethane according to comparative example DP-4 was diluted with 40.1 wt. parts of methoxypropanol (0.07% in terms of polyurethanes) and 513.3 wt. parts of deionized water, and heated to 80 ° C. Once the content of the reactor was heated to 80 ° C, 1.1 wt. parts of ammonium peroxodisulfate was dissolved in 36.4 wt. portions of deionized water were added to the reactor at standard pressure. Further, while constantly mixing, according to comparative examples D-A5 and D-A6, a mixture of 108.3 wt. parts of styrene, 189.4 wt. parts of hydroxypropyl methacrylate, 54.6 wt. parts of n-butyl acrylate, 81.1 wt. parts of methyl methacrylate, 108.3 wt. parts of tert-butylcyclohexyl acrylate and an additional 4.5 wt. parts of allyl methacrylate (0.87 mol% in terms of total vinyl monomer) together with 186.0 wt. parts of N-methylpyrrolidone was uniformly added throughout the course of five hours. With the beginning of adding a mixture of monomer, a solution of 2.2 wt. parts of ammonium peroxodisulfate in 72.8 wt. parts of deionized water were likewise added over five hours. During free radical polymerization, at intervals of 30 minutes, the content of free monomers was determined similarly to the previous example by gas chromatography, and the highest total content of monomers in terms of dispersion was determined after 30 minutes, which should be 0.6 wt. % (3.7 wt.% In terms of vinyl monomer).

After the dosed addition of monomer and initiator was completed simultaneously, the resulting reaction mixture was stirred at 80 ° C for an additional hour and then cooled to room temperature.

The resulting primary copolymer dispersion had good storage stability. Its solids content was 33.0 wt. %, the acid number was 20.1 mg KOH / g solids content and the pH was 7.0. Particle size (z average) measured by photocorrelation spectroscopy was 72 nm. Analogously to example D-A1, by gas chromatography, the content of 2.1 wt. % methoxypropanol and 6.0 wt. % N-methylpyrrolidone.

Analogously to example D-A1, the gel content, determined gravimetrically after extraction with tetrahydrofuran, was 42.1 wt. %

Example D-C1

Obtaining the invented starting dispersion of a polyetherurethane-polyacrylate copolymer derived from saturated polyetherurethane

To obtain the initial dispersion of the invented copolymer, in a nitrogen atmosphere, 1496.7 wt. parts of polytetramethylene oxide-containing dispersion of polyurethane according to the example of obtaining D-P3 was diluted with 40.0 wt. parts of methoxypropanol (0.07% in terms of polyurethane) and 1150.9 wt. parts of deionized water, and heated to 80 ° C. Once the content of the reactor was heated to 80 ° C, 0.6 wt. parts of ammonium peroxodisulfate dissolved in 35.7 wt. parts of deionized water were added to the reactor at standard pressure. Further, while constantly stirring, a mixture of 301.6 wt. parts of methyl methacrylate, 261.6 wt. parts of n-butyl acrylate, 5.6 wt. parts of allyl methacrylate (0.87 mol%) and 134.9 wt. parts of N-methylpyrrolidone was uniformly added throughout the course of six hours. With the start of adding a mixture of monomer, a solution of 1.1 wt. parts of ammonium peroxodisulfate in 71.3 wt. portions of deionized water were also added over six hours. After the dosed addition of monomer and initiator was completed simultaneously, the resulting reaction mixture was stirred at 80 ° C for an additional hour and then cooled to room temperature.

The resulting primary copolymer dispersion had very good storage stability. Its solids content was 32.8 wt. %, the acid number was 23.2 mg KOH / g solids content and the pH was 6.2. Analogously to example D-A1, by gas chromatography, the content of 1.1 wt. % methoxypropanol and 3.9 wt. % N-methylpyrrolidone. The particle size (z average) measured by photocorrelation spectroscopy was 103 nm. Analogously to example D-A1, the gel content, determined gravimetrically after extraction with tetrahydrofuran, was 85.2 wt. %

Transmission electron microscopy on unpigmented polymer films of isoprene-containing polyurethane-polyacrylate copolymers

To study morphology, free films of the initial dispersions were obtained, and they were contrasted using osmium tetroxide and examined using a transmission electron microscope.

For this purpose, one drop of the initial dispersion in each case was added to 10 ml of deionized water and mixed well. Next, a copper mesh surface was used to capture one drop of the highly diluted initial dispersion thus formed, and the polymer film was dried under high vacuum. This was accompanied by film contrasting in an atmosphere enriched with osmium tetroxide in a closed vessel.

Analysis by electron microscopy was performed in light transmission (tab. 1, Fig. 1). It included the visualization of spectral particles having a particle size of less than 150 nm in a continuous matrix of dark or light appearance, which corresponds to the core-shell morphology:

The experiment above shows that the core / shell structure of the inventive dispersion copolymers (D-B3) is the opposite of the prior art copolymer structure (D-A3).

Obtaining silver water-borne base coatings

The components listed in tables 2a, 2b, 3a and 3b under the "aqueous phase" are mixed together in the sequence set to obtain an aqueous mixture. In the next step, the components listed under the "organic phase" are used to produce the organic mixture. The organic mixture is added to the aqueous mixture. The mixture was then stirred for 10 minutes and adjusted with deionized water and N, N-dimethylethanolamine (from BASF SE) to a pH of 8.0 and a viscosity suitable for spraying.

Comparative experiments between water-borne coating bases BL-A0 - BL-A5 with the invented water-borne coating bases BL-B1 - BL-B4 regarding the limit of occurrence of pin punctures, the number of pin holes and the distinguishability of layer intersections in multilayer paint systems

In order to determine the limit of the occurrence of pinholes, the number of pinholes and the ability to hide layer intersections, multilayer colorful systems containing water-borne BL-A0 - BL-B4 coating bases were investigated.

Moreover, the water-borne coating base BL-A0 contained Foamstar MF 324 (from Cognis) and 1-octanol (from BASF SE), all other water-borne coating bases BL-A1 - BL-B4 were free of these two components.

In order to determine the limit of occurrence of pin punctures and the number of pin holes, multilayer colorful systems were made with water-borne coatings according to the following main method:

A steel panel measuring 30 cm × 50 cm coated with a filler primer was provided with a thin strip of adhesive along one longitudinal edge, in order to be able to determine the differences in layer thickness after coating. A water-borne coating base was applied electrostatically in a wedge-shaped form. The resulting film of a water-borne coating base was evaporated at room temperature for one minute and then dried at 70 ° C. in an oven with air circulation for 10 minutes. Typically, a two-component self-healing coating is applied to a dried film of a water-borne coating base. The resulting self-healing coating film was vaporized at room temperature for 20 minutes. Then, the film of the water-borne coating base and the film of the self-healing coating were kept together in an oven with air circulation at 140 ° C. for 20 minutes. The film layer thickness of the aged self-healing coating was constant (± 1 μm) over the entire sheet, with a film thickness of the self-healing coating 38-42 μm.

After a visual assessment of the tiny holes in the resulting wedge-shaped multilayer paint system, the coating thickness was determined for the limit of occurrence of pinholes.

In addition, the ability to hide layer intersections was compared:

For this purpose, a coil rolled into a spiral measuring 30 × 60 cm was painted with putty and the putty was subjected to heat treatment at 160 ° C for a period of 20 minutes. A piece of abrasive paper having 800 particles per cm ² surface was used to polish the intersection on a sheet that has a depth of 2-4 μm and a furrow width of 2 cm. Then, the corresponding coating base was applied with a coating thickness of 8-12 μm. Then, the resulting panel was dried at 80 ° C. for 10 minutes, and a conventional and well-known two-component self-healing coating was applied to the dried film of a water-borne coating base. Then, the film of the water-borne coating base and the film of the self-healing coating were kept together in an oven with air circulation at 140 ° C. for 20 minutes.

The distinguishability of the intersections of layers in a multilayer paint system was determined visually and evaluated on a scale of 1 to 5. On this scale, a high numerical indicator means good distinguishability of the intersections of the layers and a low numerical indicator good masking of intersections of the layers.

Tables 4 and 5 give an overview of the results of determining the limit of occurrence of point punctures, the number of point holes and the ability to hide layer intersections for multilayer paint systems:

Comparative tests between water-borne coatings BL-C1 - BL-C3 and invented water-borne coatings BL-C4 - BL-C7 for improved cross-sectional results

In order to determine the cross-section, multilayer colorful systems were studied containing comparative water-borne coating bases BL-C1 - BL-C3 and invented water-borne coating bases BL-C4 - BL-C7.

This was done using a panel measuring 10 cm × 20 cm, which had a primer-putty coating of a standard commercial primer-putty, as a substrate. During the production of this substrate, the filler primer was indirectly dried at 80 ° C for a period of 10 minutes and then subjected to heat treatment at 190 ° C for a period of 30 minutes.

First of all, the base material of the coating according to table 6, in each case, was applied to the panel pneumatically. After the coating base material, which was evaporated at room temperature for 1 min, the coating base material was dried indirectly in an oven with air circulation at 70 ° C for a period of 10 minutes. Then, the material of the two-component self-healing coating FF99-0345 commercially available from BASF was similarly applied pneumatically and, after evaporation at room temperature for 20 minutes, the two layers were subjected to heat treatment at a temperature of 160 ° C for a period of 30 minutes. The result was a heat-treated multilayer paint system.

After cooling the heat-treated multilayer ink system, the ink systems were cleaned. Then, a particular coating base material according to table 3 was applied pneumatically. After the coating base material, which was vaporized at room temperature for 1 minute, the coating base material was dried indirectly in an oven with air circulation at 70 ° C for a period of 10 minutes. Then, a two-component refinished self-healing coating material consisting of FF23-0500 and SC29-0093 commercially available from BASF was applied pneumatically and, after evaporation at room temperature for 20 minutes, two layers were subjected to heat treatment at a temperature of 80 ° C for a period of 30 min The result was a newly finished colorful system.

Adhesion was investigated on a partially heat-treated, newly finished coating of a paint system, a worn-out, heat-treated multilayer paint system, and a cross-sectional test.

The cross-sectional test was carried out in accordance with DIN 2409. The results of the cross-sectional test were evaluated in accordance with DIN EN ISO 2409.

Table 6 gives an overview of the cross-sectional test results with a comparison of various water-borne coating base materials:

Claims (36)

1. An aqueous dispersion for producing coating materials, comprising at least one copolymer, the copolymer obtained by (I) initially loaded with an aqueous dispersion of at least one polyurethane, and then (II) polymerizing a mixture of olefinically unsaturated monomers in the presence of polyurethane from (I), Where (a) apply a water-soluble initiator in an amount of from 0.05 to 20 wt. % in terms of the total number of olefinically unsaturated monomers, (b) the metered addition of olefinically unsaturated monomers is carried out in such a way that a concentration of 6.0 wt. %, in terms of the total number of olefinically unsaturated monomers in the reaction solution is not exceeded during the entire duration of the reaction, and (c) the mixture of olefinically unsaturated monomers comprises at least one polyolefinically unsaturated monomer. 2. The aqueous dispersion according to claim 1, where the dosed addition of olefinically unsaturated monomers is carried out in such a way that a concentration of 5.0 wt. %, in terms of the total number of olefinically unsaturated monomers, in the reaction solution is not exceeded during the entire duration of the reaction. 3. The aqueous dispersion according to claim 2, where the dosed addition of olefinically unsaturated monomers is carried out in such a way that the concentration is 4.0 wt. %, in terms of the total number of olefinically unsaturated monomers, in the reaction solution is not exceeded during the entire duration of the reaction. 4. The aqueous dispersion according to any one of paragraphs. 1-3, where the mixture of olefinically unsaturated monomers contains 0.1-6.0 mol% polyolefinically unsaturated monomers. 5. The aqueous dispersion of claim 4, wherein the mixture of olefinically unsaturated monomers contains 0.1-2.0 mol% of polyolefin unsaturated monomers. 6. The aqueous dispersion of claim 4, wherein the olefinically unsaturated monomer mixture contains 0.1-6.0 mol% allyl methacrylate and does not additionally contain any polyolefinically unsaturated monomers. 7. The aqueous dispersion of claim 6, wherein the olefinically unsaturated monomer mixture contains 0.1-2.0 mol% allyl methacrylate and does not additionally contain any polyolefinically unsaturated monomers. 8. The aqueous dispersion according to any one of paragraphs. 1-3, 5-7, where the mixture of olefinically unsaturated monomers contains <10.0 wt. % vinyl aromatic monomers, calculated on the total number of olefinically unsaturated monomers. 9. The aqueous dispersion of claim 8, wherein the mixture of olefinically unsaturated monomers contains <5.0 wt. % vinyl aromatic monomers, calculated on the total number of olefinically unsaturated monomers. 10. Aqueous dispersion according to any one of paragraphs. 1-3, 5-7, 9, where the mixture of olefinically unsaturated monomers does not contain any vinyl aromatic monomers. 11. The aqueous dispersion according to any one of paragraphs. 1-3, 5-7, 9, where the aqueous dispersion has a gel content of 40-90 wt. %, calculated on solid particles in the dispersion. 12. The aqueous dispersion according to any one of paragraphs. 1-3, 5-7, 9, where the copolymer contains at least (A) a core comprising at least one polyurethane, and (B) a shell comprising at least one polymer, which was obtained by polymerization of olefinically unsaturated monomers. 13. The use of an aqueous dispersion according to any one of paragraphs. 1-12 to obtain coating materials. 14. A water-borne base coating comprising an aqueous dispersion according to any one of paragraphs. 1-12. 15. A method of obtaining a multilayer color and / or for the effect of a colorful system in which (I) a pigmented water-borne basecoat is applied to the base, (II) form a polymer film from a coating material deposited in stage (I), (III) apply a self-healing coating to the base coat layer thus obtained, and then (IV) the basecoat layer is cured together with the self-healing coating layer, which includes the use in step (I) of a pigmented water-borne basecoat, said basecoat comprising an aqueous dispersion according to any one of claims. 1-12. 16. The use of a water-borne basecoat according to claim 14 for coating automotive bodies and / or plastic parts for installation on automotive bodies. 17. A method of obtaining an aqueous dispersion, characterized by stages of obtaining: (I) initially loaded with an aqueous dispersion of at least one polyurethane, and then (II) polymerizing a mixture of olefinically unsaturated monomers in the presence of polyurethane from (I), Where (a) a water soluble initiator is used, (b) the metered addition of olefinically unsaturated monomers is carried out in such a way that a concentration of 6.0 wt. %, in terms of the total number of olefinically unsaturated monomers in the reaction solution is not exceeded during the entire duration of the reaction, and (c) the mixture of olefinically unsaturated monomers comprises at least one polyolefinically unsaturated monomer.

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